Mineral oil compositions



Patented Nov. 25, 1952 UNITED STATES RATENT OFFIQE MINERAL OIL COMPOSITIONS Maine No Drawing. Application March 3, 1949, Serial N0. 79,514

Claims.

This. invention relates to novel lubricating oil compositions. More particularly; it is concerned with gear. oils and, especially, with universal gear lubricants.

A satisfactory universal gear lubricant is capable: of lubricating: automotiveand truck hypoids while performing at the. same: time as a reasonably satisfactory lubricant for the other gears and transmissions. found. in such vehicles. Accordingly, the problem is to provide a singular gear lubricating composition which is satisfactory for theconditions. encountered at high speedlow torque operations onone hand and, conversely, at high torque-low speed operations on the other. In addition, these lubricants must be effective without objectionable channeling, rusting, corrosion, foaming; or additive separation in various environments.

In. our copending application, Serial No, 79,513, filed concurrently herewith, we have described and claimed. new compositions. of' matter resulting fromthe reaction of a bicyclic terpene, sulfur, and a phosphorus sulfide with an alkylated phenol or an alcohol. We have now discovered that the compounds to which this application is directed are especially effective inv compounding highly satisfactory gear lubricating compositions when such products areused in conjunction. with an. organic chlorine-containing compound.

lhe proportions of the addends used in the compounding of our improved gear lubricants may be varied somewhat, but in. any case only a minor proportion of each isused. The optimum proportions to be used will depend upon the use to which the gear lubricatin composition is to be put as well as being dependent upon the particular new compositions of matter and the organic chlorine-containing compound selected. However, where, for facility of transportation or storage, the lubricant is not compoundedasa finished product, theadditive concentrations may be substantial.

Generally, the range of the. concentration of the compounds We have described. in the aforementioned" application is most satisfactory from 4 to 12% by weight on the compounded lubricant. However, we prefer and recommend an addition of about 8%.

The range of concentrations of the chlorinecontaining compounds ismost satisfactory from about Sto 8%, and is dependent in great part upon the chlorinated hydrocarbon employed.

The characteristics of the compounds to which our oopending application is directed vary somewhat, depending upon the natureand' proportions of the various reactants used. However, the compounds are generally relatively acidic and are highly soluble in mineral oils. In the formation ofthese compounds, the condensation reaction product of the phosphorus sulfide and bicyclie terpene is sulfurized and then reacted with an alkylated phenol or an alcohol. However, the bicyclic terpene alone may be sulfurized, then reacted with phosphorus sulfide, and finally with the phenol or alcohol.

A bicyclic terpene; for example, alpha-pinene, is initially contacted with a phosphorus sulfide, preferably phosphorus pentasulfide. The reaction thus effected proceeds spontaneously upon a slight heating, since it is of an exothermic nature. A desirable method of instituting this reaction is to heat the alpha-pinene ina vessel to about 275 F., orslightly higher, and then, without further heating, slowly add the phosphorus pentasulfide While maintaining a vigorous agitation. The. heat of the reaction is considerable, and consequently, the addition should be made slowly so as to avoid the possibility of the reaction becoming uncontrollable.

After the addition is completed, it is usually necessary to apply heat externally to complete the reaction, the temperature durin this latter stage preferably being maintained at about 275 F., although a thermal environment inthe range of about 200'to 400 F. may be employed.

This mixture is then raised in temperature to about 325 F., whereupon sulfur is added-slowly. The reaction mass is further reacted at about 325 F. for a period of time, whereupon it is cooled to about 275 F. and an alkylated phenol or an alcohol added. The. mixture is finally, andmost advantageously, heated for an additional'length of time at about the sametemperature.

Since. the" compositionsthereby formed are of a highly viscous nature, even at elevated. temperatures, it is usually necessary, for ease'of handling, to add a solvent-treated Mid-Continent neutral oil or other light petroleum fraction; 1

As an alternativeprocedureinpreparing these compositions, the alpha-pinenemay be initially sulfurized, e. g., the sulfur is added to alphapinene at a temperature of about. 3.00"? F. Upon completion of the addition, the reactants are heated at the same temperature for a period of timein order that the reaction isc'omplet'ed'. The mixture is then cooled. to about 275 E, whereupon the phosphorus pentasulfid'e. is. added slowly while avigorous' agitation. is: maintained. Here again? the. exothermic nature of the process dictates a. slow additionso as to avoid the possibility of the reaction becoming uncontrollable. In order to complete this reaction, the mixture is preferably further heated, whereupon an alkylated phenol or an alcohol is then added and the resulting mixture again heated for a length of time. A light oil, as described thereinbefore, is then advantageously admixed with the compound so as to promote ease of handling.

The molar relation of alpha-pinene to phosphorus pentasulfide may vary considerably. However, a molar ratio of alpha-pinene to phosphorus pentasulfide, resulting in highly desirable compounds is within the range of about 3:1 to :1. Pure alpha-pinene is preferred in preparing these compositions; however, a reactant comprising substantially alpha-pinene in admixture with other related terpenes, such as camphenes and dipentenes, is satisfactory.

The proportions of the sulfur employed may be varied over a wide range, depending upon the properties of the finished composition desired. Based upon the amount of phosphorus pentasulfide utilized, the addition of the sulfur may preferably be in the range of about 0.5: 1 to about 5:1.

The optimum proportion of the alkylated pelmol or alcohol used is to a considerable extent dependent upon the ratio of alpha-pinene to phosphorus pentasulfide. Generally satisfactory results have been obtained by employing a ratio of an alkylated phenol to phosphorus pentasulfide of about 0.25:1 to about 2:1. The alkylated phenols employed are most advantageously para-tertiary amyl phenol and paracyclohexyl phenol. However, other alkylated phenols containing from three to fifteen carbon atoms in the alkyl groups may be utilized. Exemplary are isopropyl phenol, tertiary-butyl henol, di-secondary ampyl phenol, di-tertiary amyl phenol, di-isobutyl phenol, tri-isobutyl phenol and the like. In addition, alcohols, such as 2-ethylbutyl alcohol, octanol-l, 2-ethylhexy1 alcohol, capryl alcohol and the mixture of decyl, dodecyl and tetradecyl alcohols derived from coconut oil may also be used to replace part or all of the alkylated phenol. However, the alkylated phenols are preferred.

The exact mechanism of the reactions forming these compounds is unknown, nor has a molecular weight or structure been assigned to them because of their complexity. The following are specific examples of the compositions and illustrate the procedure by which they may be successfully prepared.

Example A 2176 gms. (16 moles) of alpha-pinene were charged into a five-liter, three-necked flask equipped with a mechanical stirrer and a thermometer. The alpha-pinene was heated to 275 F. with an electric heating mantle, whereupon the heat was turned off. 888 gms. (4 moles) of phosphorus pentasulfide were added portionwise, over a 2 /2 hour period accompanied with vigorous stirring, the heat of the reaction maintaining the temperature in the range of 275 F. to 290 F. The reaction mixture was heated an additional two hours at 275 F. Then the temperature was raised to 325 F. and 192 gms. (6 atoms) of sulfur were added in three equal portions. After the final addition of sulfur, the temperature rose to 361 F. because of the exothermic nature of the reaction. The mixture was cooled to 325 F. and held at 325 to 335 F. for six hours. 1628 gms. of the reaction mixture, one half of the total, were removed from the flask, and to the balance were added 246 gms. (1.5 moles) of paratertiary amyl phenol. The reaction mass was heated for ten hours at 275 F., following which, an oil concentrate was prepared by dissolving the prouct formed in 2058 gms. of a solventtreated Mid-Continent neutral oil, and the solution filtered with filter aid. An analysis of theoil concentrate thus prepared indicated that it contained 2.72% phosphorus and 10.56% sulfur and had an acid number of 6.5 and a saponification number of 68.0.

Example B 1088 gms. (8 moles) of alpha-pinene were charged into a five-liter, three-necked flask and heated to 275 F. The heat was turned off and 444 gms. (2 moles) of phosphorus pentasulfide were added over a. one-hour period accompanied with vigorous stirring, the heat of reaction maintaining the temperature at 275 to 290 F. The reaction mass was heated an additional two hours at 275 F. and then raised to 325 F. 96 gms. (3 atoms) of flowers of sulfur were added and the reaction mixture heated for six hours at 325 to 335 F. After cooling to 275 F., 246 gms. (1.5 moles) of para-tertiary amyl phenol were added and the reaction mass heated for ten hours at 275 to 280 F. 2058 gms. of the neutral oil were added to the compound formed and mixing was continued for one-half hour. gms. of a filter aid were further added and the product was filtered. An analysis of the oil concentrate thus prepared indicated that it contained 3.10% phosphorus, 10.84% sulfur and had an acid number of 5.4 and a, saponification number of 71.4.

Example C To 544 gms. (4 moles) of alpha-pinene, heated to 275 F., were added 222 gms. (1 mole) of phosphorus pentasulfide in small portions so that the heat of reaction maintained the reaction at 275 F. After all the phosphorus pentasulfide had been added, the reaction mass was heated at 275 F. for seven hours and then raised to 325 F. 64 gms. (2 atoms) of sulfur were added and the mixture then maintained at 325 F. for six hours. After cooling to 275 F., 123 gms. (0.75 mole) of para-tertiary amyl phenol were added. The reaction mass was then heated for ten hours at 275 F. 1029 gms. of the neutral oil were added to prepare an oil concentrate. An analysis of the oil concentrate thus prepared indicated that it contained 3.00% phosphorus and 10.73% sulfur and had an acid number of 5.8.

Example D The composition prepared in this example was formed by the procedure described in Example B, except that the temperature range maintained during the reaction with sulfur was 3ZO- '-5 F. and the reaction time after the addition of the para-tertiary amyl phenol was nine hours. An analysis of the oil concentrate thus prepared indicated that it contained 3.08% phosphorus and 10.68% sulfur and had an acid number of 7.2 and a saponification number of 65.0.

Example E The composition prepared in this example was formed by the procedure described in Example D, except that the reaction time after the addition of the para-tertiary amyl phenol was five hours. An analysis of the oil concentrate thus prepared indicated that it contained 2.98% phos- '5 phorus and 10.60% sulfur and had an acid number of 7.5 and a saponification number of 65.6.

Example F The composition prepared in this example was formed by the procedure described in Example D, except that the reaction time after the addition of the para-tertiary amyl phenol was fifteen hours. An analysis of the oil concentrate thus prepared indicated that it contained 2.94% phosphorus and 10.46% sulfur and had an acid number of 6.7 and a saponification number of 71.7.

Example G 4352 gms. (32 moles) of alpha-pinene were charged into a twenty-two liter, three-nicked flask equipped with a thermometer, motor driven stirrer, and electric heating mantle and heated to 275 F. The heat was turned off and 1776 gms. (8 moles) of phosphorus pentasulfide were added slowly, over a two-hour period accompanied with vigorous stirring, the temperature being maintained at 275 to 290 F. because of the exothermic nature of the reaction. After all the phosphorus pentasulfide had been added, the reaction mass was heated to 275 F. for one hour longer, and then raised to 320 F. 384 gms. (12 atoms) of sulfur were then added, and the temperature held at 315 to 320 F. for six hours. During the next hour, the temperature was lowered to 275 F. and 1056 gms. (6 moles) of paracylcohexyl phenol were added. The reaction was continued at 275 to 280 F. for ten hours and then at 305 to 320 F. for five hours. 8160 gms. of the neutral oil were then added and the product filtered. An analysis of the oil concentrate thus prepared indicated that it contained 3.11% phosphorus and 10.58% sulfur and had an acid number of 5.3 and a saponification number of 65.6.

Example H 1360 gms. moles) of alpha-pinene were heated to 300 F. in a five-liter, three-necked flask equipped with a mechanical stirrer and a thermometer. 192 gms. (6 atoms) of sulfur were added, and the reactants heated for three hours at 300 F. The reaction mass was cooled to 275 F., and with the heat turned off, 444 gms. (2 moles) of phosphorus pentasulfide were added portionwise over a 1 /4 hour period, the heat of reaction maintaining the temperature at 275 F. Heating at 275 F. continued for two hours, and at 300 F. for three additional hours.

To one-fourth of the intermediate reaction product were added 88 gms. (0.5 mole) of paracyclohexyl phenol, and the reaction mass was then heated for 9 /2 hours at 300 F. 483 gms. of the neutral oil were then added and the product filtered, using a small amount of a filter aid. An analysis of the oil concentrate thus prepared indicated that it contained 2.96% phosphorus and 11.64% sulfur and had an acid number of 6.5 and a saponification number of 64.2.

Example I To the remaining three-fourths of the intermediate prepared in Example H by the reaction of sulfurized alphapinene with phosphorus pentasulfide, heated to 280 F., were added 246 gms. (1.5 moles) of para-tertiary amyl phenol. The reaction period was 9 /2 hours at 300 F. 1196 gms. of the neutral oil were added thereto, as was a filter aid, and the oil concentrate soformed was then filtered. An analysis of the oil con- 6 centrate thus prepared indicated that it contained 3.08% phosphorus and 12.97% sulfur and had an acid number of 8.2 and a saponification number of 71.9.

Example J 288 gms. (9 atoms) of sulfur and 1360 gms. (10 moles) of alpha-pinene were heated for three hours at 300 to 305 F. in a five-liter, threenecked flask provided with a mechanical stirrer and a thermometer. The reaction mass was cooled to 275 F., and with the heat turned off, 444 gms. (2 moles) of phosphorus pentasulfide were added portionwise over a two-hour period, the heat of reaction maintaining the temperature at 275 to 285 F. The reaction continued for one hour at 275 F. and for three hours at 300 F. 410 gms. (2.5 moles) of para-tertiary amyl phenol were added and reacted for ten hours at 300 F. 1418 gms. of the neutral oil were then introduced so as to form an oil concentrate which was then filtered. An analysis of the oil concentrate thus prepared indicated that it contained 3.42% phosphorus and 15.66% sulfur and had an acid number of 14.5 and a saponification number of 80.2.

Various chlorine containing hydrocarbons may be used in preparing these improved novel lubricating compositions; the intended use of the lubricant is determinative of the nature and characteristics of the chlorinated addends. Chlorinated naphthalenes and chlorinated paraffin waxes are illustrative of highly desirable compounds of this nature. In addition, chlorinated diphenyls may be used. In each case, the important considerations are the effective amounts of chlorine available and the solubility of the selected additive in oil. Generally, chlorinated naphthalenes and parafiin waxes having a. minimum tendency to evolve free hydrogen chloride in storage or upon moderate heating are compounds most advantageously employed in the preparation of the lubricants.

The chlorine content of the chlorinated naphthalenes and the chlorinated parafiin waxes will vary greatly and amounts ranging from about 50 to chlorine in naphthalenes and about 35 to chlorine in paraffin waxes have been found to be satisfactory. However, the criteria for determining the efiicacy of a chlorine-containing substance, as mentioned above, appear to be primarily dependent upon the effective amounts of chlorine available and the solubility of the compound in the oil.

The range of concentration of these compounds in the improved lubricating composition is most satisfactory from about 3 to 8% by weight on the compounded lubricant. In particular, 6% of a chlorinated paraffin wax containing approximately 40% chlorine has been found to be high- 1y satisfactory.

To further illustrate our invention, various lubricating compositions have been compounded and tested. The standard federal specified methods for evaulating the performance of universal gear lubricants, which we have used, are described in the Coordinating Research Council Handbook, 1946 edition. In addition, certain other tests, namely, the Timken weed-out procedures were resorted to. These latter tests are performed essentially as follows:

The Timken L20 weed-out procedure No. 1.-- Timken L-20 weed-out procedures employ the Timken testing machine of the Coordinating Research Councils Timken machine test (C'RC' L-18-545) with necessary modifications as required to operate under the following conditions:

Test cup speed 100 R. P. M.

Lever load 198 pounds Oil temperature 250 F.

Oil feed Rapid circulation over entire cup Duration 16 hours The total weight loss of the test cup and block are determined and these parts are examined for failure.

The Timken L-20 weed-out procedure N0. 2. This test is identical with procedure No. 1 except that the test block is continuously moved back and forth beneath the test cup in a direction paralleling the lever arm for a distance of 0.13 inch four times per minute. In addition, the coeificient of friction and sludge formation, particularly of deposits on the Timken test block, are recorded during the 16-hour wear test.

Additional one-hour tests are made at higher speeds. These tests indicate the maximum R. P. M. to the nearest R. P. M. at which 198 pounds can be carried for one hour without any evidence of failure by scoring, grooving, or smearing. The Timken L-20 procedure No. 2 is preferred over procedure No. 1 because wear occurs under line contact conditions at unit loads closely simulating those in hypoid gears under high torque conditions. Uncompounded base oils will usually fail at from 25 to of the regular 198-pound lever load. Commercial hypoid gear lubricants Which meet standard specifications give from 4 to 15 mgs. of wear and a smooth, bright surface. Commercial hypoid gear lubricants which pass the CBC high speed axle test but fail the CRC high torque axle test show from to 300 mg. of wear and heavy grooving.

The following examples illustrate various universal gear lubricating compositions, as well as the results of certain evaluating tests performed upon each lubricant. In Compositions I to XIII the reaction product and the chlorinated hydrocarbon were blended with a base oil as identified in the table. In Compositions XIV and XV the neutral and bright stock oils identified were Mid- Continent solvent-treated petroleum fractions. Since the lubricant was found to be highly satisfactory in the latter two compositions, general properties of the composition are listed. The pour depressant compounded into the lubricating oil compositions was an octadecyl methacrylate polymer. The antifoam agent was a silicone polymer, while the solubilizer was a 10% concentrate of calcium sulfonate in oil. Compositions VIII, IX, and X contained 1% of this additive, which was intended for use principally as a solubilizer, although the addend has utility also as a rust and sludge inhibitor. However, the presence of the compound is not critical, since its functions are not essential to the practice of our invention. In particular, the Timken procedures in the aforementioned examples VIII, IX, and X indicate that 1% of the sulfonate concentrate does not appreciably affect load capacity. However, appreciable amounts, for instance 5% or more, will undoubtedly decrease the load capacity, chemical activity, and the oxidation sludging of the lubricant.

A preferred alpha-pinene-sulfur-phosphorus pentasulfide-alkylated phenol compound is the preparation of Example F. Although this compound contains the same molar ratio of reactants as of Example A, the total reaction time for the preparation is longer, which results in a noticeable improvement with respect to stability to oxidation and hydrolysis. Another preferred compound is that of Example G which exhibits similar valuable properties as that of Example F. Preferred universal gear lubricants are illustrated by Compositions XIV and XV, which satisfactorily passed all evaluation tests.

TABLE Composition Mid-Continent solvent-treated neutral oil,

weight percent 16.97 Mid-Continent solvent-treated bright stock oil, weight percent 82.83 Pour depressant, weight percent 0.20

Properties Flash point, "F 460 Viscosity, S. U. S. at "F 1216 210 "F 96 Viscosity index 91 Pour point, F -5 Sulfur, percent 0.28

Composition I The lubricating oil composition was composed of by weight:

Percent Preparation of Example A 8 Base oil 92 When this composition was tested by the Timken L20 weed-out procedure No. 1, there was a 9 mg. loss after 16 hours of wear and the surfaces revealed a light grooving. As a result this lubricant received a borderline rating in the test. The copper strip activity test (CRC L-16-445) revealed a dark peacock color after 1 hour at 250 F. There was no rust formation in the rust protection test (CRC Ll3-445).

Composition II The lubricating oil composition was composed of by weight:

Percent 70% Clz-containing paraffin wax 3.6

Base oil 96.4

The lubricant did not pass the Timken procedure No. 1, since there was an 82 mg. loss after 16 hours of wear, and the surfaces were heavily grooved.

Composition III The lubricating oil composition was composed of by weight:

Percent 57% Ola-containing naphthalene 6 Base oil 94 The Timken procedure No. 1 showed a 52 mg. loss after 16 hours of wear, with smeared surfaces. Accordingly, the lubricating composition did not pass this test. The copper strip was not stained after 1 hour at 250 F., and there was a light rust when the oil was tested according to the rust protection test. The channeling test (CRC 11-15-445), conducted at 15 F., was satisfactorily passed by the lubricant.

Composition IV The lubricating oil composition was composed of by weight:

Percent Preparation of Example A 8 42% Clz-cOIltfliIliIlg paraffin wax 1.5 Base oil 90.5

Composition V The lubricating oil composition was composed of by weight:

Percent Preparation of Example B 4 57% Ola-containing naphthalene 6 Base oil 90 The Timken procedure No. 1 showed a 7. mg. loss after 16 hours of wear. and the surfaces were in good condition. The gear lubricant, accordingly. passed this test. The color of the. copper strip after 1 hour at. 250 F. was dark peacock. There was no rust formation in the. rust protection test.

Composition. VI.

The lubricating oil composition was. composed of by weight:

Percent Preparation of Example. B. 8

70% Clz-containing parafiin wax 3.6

Base oil 88.4

The Timken procedure No. 1 showed an. 18 mg. loss after 16 hours of wear, with the surfaces in fair condition. The lubricant passed this test.

Composition VII The lubricating oil composition was composed of by weight:

Percent Preparation of Example I 4 42% Clz-containing parafiin wax 3 Base oil 93' The Timken procedure N'o.v 1 showed; a. 10 mg. loss after 16 hours of wear, and the surfaces. were lightly grooved. The lubricant was on the borderline of passing this test. The copper strip was a. light peacock color after 1. hour at 250. F., while no rust wasv formed in the rust. protection test.

Composition VIII The lubricating oil composition was composed of by weight:

Percent Preparation of Example H 2 57% (Hz-containing naphthalene 6 Solubilizer -1 1' Base oil 91 The Timken procedure No. 1 showed a 4 mg. loss after 16 hours of wear, and the surfaces were in good condition. Asa result the gear oil passed.

this test. After 1 hour at 250 F., the. copper strip wasv a light peacock color. The rust'protection test revealed no rust formation- C'omposition IX The lubricating oil composition was composed of by weight:

Percent- Preparation of Example H 4 57% Clz-containing naphthalene 6.

Solubilizer 1' Base oil 89- acrenca The Timken procedure No. 1 showed a 3 mg. loss after 16 hours of weanthe surfaces. being in good condition. The composition passed this test. After 1 hour at 250 F., the copper strip was a dark peacock color. formed in the rust. protection test. The lubricant satisfactorily passed the channeling test at -15 F.

Composition X The lubricating: oil composition was. composed of by weight:

Percent Preparation ofExample J 4' 57% Ch-containing naphthalene 6 Solubilizer 1 Base oil 89 The Timken procedure No. I showed an 8. mg. loss after 16' hours of wear, the surfaces being in good condition. The composition passed this test. The copper strip was a, dark peacock color after 1 hour at 250 F; No rust formed during the rust protection test. The channeling test at -.-l5 F. was. passed.

Composition XI The lubricating oil composition was; composed of by Weight:

Percent Preparation of ExampleF 8 57% Clz-containing naphthalene 6 Base. oil. 86

The Timken procedure No. 2 showed a 13 mg. loss after 16 hours of wearand the surfaces were in good condition- The coefficient of friction was 0.09 and the safe. R. P. M. were 2.50.. The gear. lubricant, accordingly, passedthis test. The col-- or ofthe copper strip after 1' hour at 250 F. was

dark peacock. There Wasno rust formation in.

the rust protection test.

Composition XII The lubricating oil composition was composed of by weight:

Percent Preparation of Example I 8 42% Clz-containing parafiin wax 6 Base oil 86 The Timken procedure No. 1 showed a 10 mg. loss after 16 hours of- Wear, and the surfaces were in. good condition. The lubricant passed this test. The copper strip was a dark peacock color after 1 hour at 250 F. The rust protection test.

showed no rust formation.

Composition XIII The lubricating. oil composition was composed of by weight;

Percent Preparationof ExampleB 12 57% Ola-containing naphthalene 6 Base. oil S2 The Timkenprocedure No. 1 showed an 11 mg. loss after 6 hours of wear, and the surfaces were in good condition. The lubricant passed this test. The copper strip was a dark peacockcolor after" 1 hour at 250 F. The rust protection" test showed no rust formation.

There. was no rust- Composition XIV The lubricating oil composition was composed of by weight:

Percent Preparation of Example A 8 57% Clz-containing naphthalene 6 Bright stock oil 71.16 Neutral oil 14.58

Pour depressant 0.26 Antifoam agent 0.0005

The more important properties of this composition were:

Gravity, A. P. I 21 Flash point, F. 410 Viscosity, S. U. S. at 100 "F 1125 210 F. 90 Viscosity index 88 Pour point, "F Acid number 0.25 Phosphorus, per cent 0.217 Chlorine, per cent 3.05 Sulfur, total per cent 1.07 Suufur, base oil, per cent 0.28

The Timken procedure No. 2 showed an 8 mg. loss after 16 hours of wear, the condition of the surfaces being good. The coeflicient of friction was 0.08, while the safe R. P. M. were 250. The lubricant passed this test. In addition, the composition passed the foam test, the channeling test at 15 F., the moisture corrosion characteristics test (CRC L-21-445), the storage solubility test, the compatibility test (CRC L-22-445 modified), and the high speed axle test. The rust protection test showed no rust formation (only a gray coating) after 4 hours at 180 F., while the copper strip was a dark peacock color after 1 hour at 250 F. The S. A. E. rating (CRC L-17-545) at 1000 R. P. M. was 275 pounds, while the Timken machine test (CRC L-18-545) indicated that a 28-pound load could be withstood. The high torque axle test was passed, although the formation of some brown lacquer-like deposits on the coast side of the pinion gear were in evidence.

Composition XV The lubricating oil composition was composed of by weight:

Percent Preparation of Example G 8 40% Clz-containing parafiin wax 6 Bright stock oil 63.45 Neutral oil 22.29 Pour depressant 0.26 Antifoam agent 0.0005

The more important properties of this composition were:

Gravity, A. P. I 23.2 Flash point, F 440 Viscosity, S. U. S. at 100 F 1007 210 "F 84.4 Viscosity index 86 Pour point, F. 0

Acid number 0.40 Phosphorus, per cent 0.22 Chlorine, per cent 2.38 Sulfur, total per cent 1.09 Sulfur, base oil, per cent 0.28

The Timken procedure No. 2 showed a 12 mg. loss after 16 hours of wear, the condition of the surfaces being good. The safe R. P. M. for 1 hour were 225, and the lubricant passed the Timken procedure No. 2. The copper strip was a dark peacock color after 1 hour at 250 F., while the rust protection test indicated no rust formation (only a gray coating) after 4 hours at 180 F. This composition passed the channeling test, the high speed axle test, and the high torque axle test (CRC L-20-545). The foam test (CRC 11-12-445) was passed, sequence 1 revealing 0 cc. of foam after 5 minutes of aeration at 75 F., while sequence 2 revealed 25 cc. of foam after 5 minutes of aeration at 200 F.

We claim:

1. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 7 5% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of a bicyclic terpene, sulfur, a phosphorus sulfide, and a compound selected from the class consisting of monohydride lower alkyl phenols and alcohols in which the proportions of terpene to sulfur to phosphorus sulfide to phenol or alcohol are in the approximate molar ratio 3-5:0.55:1:0.25-2.

2. A lubricating oil composition comprising predominantly a mineral oil and containing minor but eifective proportions for extreme pressure properties of an oil soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of about 3 to 5 moles of alpha-pinene, about 0.5 to 5 atoms of sulfur, about 1 mole of phosphorus pentasulfide, and about 0.25 to 2 moles of a compound selected from the class consisting of monohydric lower alkyl phenols and alcohols.

3. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of a sulfurized condensation product of alpha-pinene and phosphorus pentasulfide with a compound selected from the class consisting of monohydric lower alkyl phenols and alcohols in which the proportions of alpha-pinene to sulfur to phosphorus pentasulfide to phenol or alcohol are in the approximate molar ratio 35:0.55:1:0.25-2.

4. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of a condensation product of sulfurized alpha-pinene, and phosphorus pentasulfide with a compound selected from the class consisting of monohydric lower alkyl phenols and alcohols in which the proportions of a1phapinene to sulfur to phosphorus pentasulfide to phenol or alcohol are in the approximate molar ratio 3-5:0.5-5:1:0.25-2.

5. A lubricating oil composition comprising predominantly a mineral oil and containing about 3 to 8% of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and 4 to 12% of a composition of matter prepared by the reaction at a temperature of about 200 to about 400 F. of a bicyclic terpene, sulfur, a phosphorus sulfide, and a compound selected from the class consisting of monohydric lower allryl phenols and alcohols in which the proportions of terpene to sulfur to phosphorus sulfide to phenol or alcohol are in the approximate molar ratio 3-5:0.5-5:1:0.25-2.

6. A lubricating oil composition comprising predominantly a mineral oil and containing about 3 to 8% of an oil-soluble stable chlorinated paraffin Wax containing about 35 to 75% chlorine and 4 to 12% of a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of alpha-pinene, sulfur, phosphorus pentasuliide, and a compound selected from the class consisting of monohydric lower alkyl phenols and alcohols in which the proportions of alpha-pinene to sulfur to phosphorus pentasulfide to phenol or alcohol are in the approximate molar ratio 3-5:0.55:1:0.25-2.

7. A lubricating oil composition comprising predominantly a mineral oil and containing 7 about 3 to 8% of an oil-soluble stable chlorinated naphthalene containing about 35 to 75% chlorine and 4 to 12% of a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of alpha-pinene, sulfur, phosphorus pentasulfide, and a compound selected from the class consisting of monohydric lower alkyl phenols and alcohols in which the proportions of alpha-pinene to sulfur to phosphorus pentasulfide to phenol or alcohol are in the approximate molar ratio 3-5:0.5-5:1:0.5-2.

8. A lubricating oil composition comprising predominantly a mineral oil and containing minor but efiective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of alpha-pinene, sulfur phosphorus pentasulfide and a monohydric lower alkyl phenol in which the proportions of alphapinene to sulfur to phosphorus pentasulfide to phenol are in the approximate molar ratio 9. A lubricating oil composition comprising predominantly a mineral oil and containing minor but eifective proportions for extreme pressure properties of an oil-soluble stable chlorinated, hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 of a sulfurized condensation product of alpha-pinene and phosphorus pentasulfide with a monohydric lower alkyl phenol in which the proportions of alpha-pinene to sulfur to phosphorus pentasulflde to phenol are in the approximate molar ratio 3 5:0.55:1:0.252.

10. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing abou 35 to 75% chlorine and a composition of matter prepared by the reaction at a temperature of about 200 F. to about 400 F. of a condensation product of sulfurized alpha-pinene, and phosphorus pentasulfide with a monohydric lower alkyl phenol in which the proportions of alpha-pinene to sulfur to phosphorus pentasulfide to phenol are in the approximate molar ratio of 3-5:0.5-5:1:0.25-2.

LEONARD BEARE. MILTON P. KLEINHOLZ. WILLIAM S. HOOCK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,254,337 Whittier Sept. 2, 1941 2,316,087 Gaynor et a1 Apr. 6, 1943 2,379,312 May June 26, 1945 2,409,877 May Oct. 22, 1946 2,415,837 Musselman et al. Feb. 18, 1947 2,468,520 Sproule et al. Apr. 26, 1949 2,481,487 Adelson Sept. 13, 1949 

1. A LUBRICATING OIL COMPOSITION COMPRISING PREDOMINANTLY A MINERAL OIL AND CONTAINING MINOR BUT EFFECTIVE PROPORTIONS FOR EXTREME PRESSURE PROPERTIES OF AN OIL-SOLUBLE STABLE CHLORINATED HYDROCARBON CONTAINING ABOUT 35 TO 75% CHLORINE AND A COMPOSITION OF MATTER PREPARED BY THE REACTION AT A TEMPERATURE OF ABOUT 200* F. TO ABOUT 400* F. OF A BICYCLIC TERPENE, SULFUR, A PHOSPHOROUS SULFIDE, AND A COMPOUND SELECTED FROM THE CLASS CONSISTING OF MONOHYDRIDE LOWER ALKYL PHENOLS AND ALCOHOLS IN WHICH THE PROPORTIONS OF TERPENE TO SULFUR TO PHOSPHORUS SULFIDE TO PHENOL OR ALCOHOL ARE IN THE APPROXIMATE MOLAR RATIO 3-5:0.5-5:1:0.25-2. 